Monoazo dyestuffs



United States Patent OfiFice 3,314,935 Patented Apr. 18, 1967 Thisapplication is a continuation-in-part of our now abandoned application,Ser. No. 144,319, which was filed in the United States Patent Office onOct. 11, 1961, and which is a continuation-in-part of, our nowabandoned, application Ser. No. 762,924, which was filed in the UnitedStates Patent Ofiice on Sept, 24, 1958.

This invention relates to monoazo dyestuffs and more particularly itrelates to disperse, i.e. water-insoluble, monoazo dyestuits which arevaluable for colouring synthetic textile materials in particularpolyamide and cellulose acetate textile materials.

According to the invention there are provided the monoazo dyestuffs ofthe formula:

S OzNI-IR Y wherein A is an arylene radical selected from the classconsisting of phenylene and naphthylene radicals, and any furthersubstituents on said phenylene radical are selected from the classconsisting of chlorine, bromine, lower alkyl, lower alkoxyand'trifiuoromethyl;

R is selected from the class consisting of fl-chloroethyl,,B-bromoethyl; fiz'y-dichloropropyl, Bw-dibromopropyl,-chloro-,8-hydroxypropyl and -brorno-fi-hydroxypropyl;

B is an arylene radical selected from the class consisting of1:4-phenylene, 1:4-naphthylene and 1:2-naphthylene radicals, and anyfurther substituents on said arylene radical are selected from the classconsisting of chlorine, bromine, lower alkyl, lower alkoxy andacetylarnino;

Y is selected from the class consisting of hydrogen, lower alkyl,hydroxy lower alkyl, acetoxy lower alkyl, and ,B-lower alkoxyethyl; andY is selected from the class consisting of hydrogen, lower alkyl,hydroxy lower alkyl, p-aminoethyl, fl-cyanoethyl, and acetoxy loweralkyl.

As examples of the lower alkyl radicals which may be present assubstituents on the said arylene radicals represented by A and B theremay be mentioned alkyl radicals containing from 1 to 4 carbon atoms, inparticular methyl and ethyl radicals. As examples of the lower alkoxyradicals which may be present as substituents on the said aryleneradicals represented by A and B there may be mentioned alkoxy radicalscontaining from 1 to 4 carbon atoms, in particular methoxy and ethoxyradicals.

As examples of the lower alkyl radicals represnted by Y and Y there maybe mentioned methyl, ethyl, propyl and butyl radicals. As examples ofthe hydroxy lower alkyl radicals represented by Y and Y there may bementioned p-hydroxyethyl and [3- or 'y-hydroxypropyl radicals. Asexamples of the ii-lower alkoxy radicals represented by Y there may bementioned B-methoxyethyl and ,B-ethoxyethyl radicals. As examples of theacetoxy lower alkyl radicals represented by Y and Y there may bementioned ,B-acetoxy-ethyl and [3- or -acetoxypropyl radicals.

The monoazo dyestuffs of the invention can be obtained by diazotising anamine of the formula:

wherein A and R have the meanings stated, and coupling the resultingdiazo compound with a coupling component of the formula:

Y1 H-B-N wherein B, if and Y have the meanings stated.

This reaction can be conveniently carried out by adding an aqueoussolution of sodium nitrite to a solution or suspension of the amine in adilute aqueous solution of hydrochloric acid or in a mixture of aceticacid and an aqueous solution of hydrochloric acid, thereafter adding theresulting mixture containing the diazo compound to a solution of thecoupling component in a dilute aqueous solution of hydrochloric acid,adding sodium acetate to increase the pH of the mixture preferably to apH of about 5, and stirring the resulting mixture to effect formation ofthe monoazo dyestuif. The monoazo dyestufi is then isolated byconventional methods.

As examples of amines of the above formula there may 0 be mentioned:

2-, 3- or 4-aminobenzenesulphon-N-(Ii-chloroethyl)- amide,

2-, 3- or 4-aminobenzenesulphon-N-(fi-bromoethyl)- amide,

2-naphthylamine-5-, 6-, 7- or S-SuIPhon-N-(B- chloroethyl) amide,

l-naphthylarnine-4-, 5-, 6- or 7-sulphon-N-(flchloroethyl amide,

3-chloro-4-arninobenzenesulphon-N-({3- chloroethyl) amide,

2 5 -dichloro-4-aminobenzenesulphon-N- flchloroethyl) amide,

2-, 3- or 4-aminobenzenesulphon-N-(' -chloro-fihydroxypropyl) amide,

2-, 3- or 4-arninObenZenesulphon-N-(y-brorno-B- hydroxypropyl) amide,

2-, 3- or 4-aminobenzenesulphon-N-(B2 dichl oropropyl) amide,

2-, 3- or 4-aminobenzenesulphon-N-(B2 dibromopropyl) amide,

2-anisidine-4-sulphon-N- (fi-chloroethyl) amide,

2-anisidine-4-sulphon-N-(' -chloro-B- hydroxypropyl) amide,

Z-anisidine-4-sulphon-N-(' -bromo-fihydroxypropyl) amide,

Z-amino-4-trifluoromethylbenzenesulphon-N-(,8-

chloroethyl) amide,

3-bromo-4-aminobenzenesulphon-N-( 8- chloroethyl) amide,

3-chloro-4-an1ino-5-methylbenzenesuIphon-N-(fichloroethyl) amide,

3 5 -dichioro-4-aminobenzenesulphon-N-( 18- chloroethyl)amide, and

2 5-dichloro-4-aminobenzenesulphon-N-('y-chloro-B- hydroxypropyl) amide.

The amines of the above formula can themselves be btained by reacting acompound of the formula:

SIOZCI vherein T represents a nitro or acetylamino group with .n amineof the formula RNH wherein A and R have he meanings stated, andsubsequently converting the group represented by T to an amino group byreduction If by hydrolysis.

As examples of coupling components of the above ormula there may bementioned:

\l N-dimethylaniline,

l N-diethylaniline,

- l-methyl-N- ,B-hydroxyethyl) aniline,

I N-di fl-hydroxyethyl) aniline,

I N-di fl-hydroxyethyl -m-toluidine,

*1 N-di(,B-hydroxyethyl) -m-chloroaniline,

I N-di B-hydroxyethyl -m-bromoaniline,

I N-di B-hydroxyethyl -2-methoxy-S-methylaniline,Z-methoxy-l-naphthyl-amine, Z-ethoxy-l-naphthylarnine,

81-(13-hydroxyethyl l-naphthylamine,

SI- B-hydroxyethyl -2-naphthylamine,

l-N- ,B-hydroxyethyl) amino-4-chloronaphthalene, l-N- (B-hydroxyethyl)amino-5 8-dichloronaphthalene,N-(fi-hydroxyethyl)-N-(fi-aminoethyl)aniline,

N- ,B-hydroxyethyl) -N- B-cy anoethyl -m-toluidine 2- [N N-diB-hydroxyethyl amino] -4-acetylaminoanisole,N:N-diethyl-3-acetylaminoaniline,

N- B-ethoxyethyl) -N- B-cyanoethyl) -m-toluidine, N- fl-hydroxyeth yl-m-toluidine, and

N: N-di (,B-acetoxyethyl) -m-toluidine.

The water-insoluble monoazo dyestuffs of the invention may be used forthe colouration of textile materials comprising ani-mal fibres such aswool, silk and regenerated protein fibres, and artificial fibres such ascelulose ester fibres for example secondary cellulose acetate andcellulose triacetate fibres, synthetic linear polyamide fibresespecially polyhexamethylene adipamide, and polycaprolactam fibres,polyurethane, polyester, polyacrylonitrile and modifiedpolyacrylonitrile fibres, by treating the textile materials with aqueousdispersions of the said dyestuffs. The aqueous dispersions of thedyestuffs may be obtained by methods known and described for dispersedyestuffs in general, for example by milling the dyestuffs in thepresence of dispersing agents for example the sodium salt of sulphonatednaphthalene formaldehyde condensation products with or without theaddition of protective colloids for example dextrin. The dyestuffs may,if desired, be converted into a dispersible powder form. Substancesknown to assist or improve dyeing, for example the dispersing agents andprotective colloids described above and electrolytes, may be added tothe dyebath.

The said dyestuffs may be applied to the textile materials at atemperature at or near the boiling point of the 'dyebath, preferably ata temperature between 75 C. and 100 C., or if desired, a highertemperature, for example a temperature between 100 C. and 130 C., may beused at superatmospheric pressure. Textile materials which are notstable at temperatures above 90 C., for example secondary celluloseacetate, are preferably dyed at temperatures between 60 C. and 85 C.

In the dyeing of cellulose triacetate or polyester textile materialswith the dyestuffs of the invention it is sometimes advantageous to usea swelling agent or other carrier material for example diphenyl,dichlorobenzene, or trichloroethylene.

The monoazo dyestuffs may also be applied to textile materials in theform of thickened printing pastes containing a fine dispersion of thedyestuffs. The printing pastes may be thickened with any of the usualthickening agents for example with methyl cellulose, locust bean gum,Nafka crystal gum, or sodium alginate, and may contain normal adjuvantsfor printing pastes such as urea, thiourea or thiodiglycol, adjuvantsfor the application of disperse dyes such as methylated spirits, sodiummetanitrobenzenesulphonate or aqueous emulsions of sulphonated oils,swelling agents or dyeing carriers such as diphenyl. The printing pastesmay be conveniently applied to the textile materials by printing withblock, spray, stencil, screen or roller, preferably drying the printedmaterials and if desired steaming at superatmospheric pressure, when atemperature above (3., preferably between 1l0= C. and C., is required.

The monoazo dyestuffs are of especial value for printing celluloseacetate textile materials.

If desired the monoazo dyestuffs, as hereinbefore defined, may beapplied to artificial textile materials in conjunction With a treatmentwith an amine, phenol or thiophenol, which may be applied to the textilematerial prior to, simultaneously with or subsequent to the applicationof the dyestuffs.

When used on textile materials comprising wool, silk or regeneratedprotein fibres or artificial fibres such as polyamide fibres orbasically modified polyacrylonitrile fibres the monoazo dyestuffs, ashereinbefore defined, give colourations distinguished by their highfastness to wet treatments and to dry heat treatments. They also haveexcellent dyeing properties, especially build-up and levellingproperties, and on this account they are of great value for applicationto barr nylon. In many cases also the said monoazo dyestuffs haveexcellent fastness to light.

A preferred class of the monoazo dyestuffs of the invention comprisesthe monoazo dyestuffs which are represented by the formula:

wherein R, B, Y and Y have the meanings stated, and any furthersubstituents on the benzene ring are selected from the class consistingof chlorine, bromine, lower alkyl, lower alkoxy and trifluoromethyl.

A second preferred class of the monoazo dyestuffs of the inventioncomprises the monoazo dyestuffs which are represented by the formula:

wherein R, Y and Y have the meanings stated; any further substituents onthe benzene ring I being selected from the class consisting of chlorine,bromine, lower alkyl, lower alkoxy and trifiuoromethyl; and any furthersubstituents on the benzene ring II being selected from the classconsisting of chlorine, bromine, lower alkyl, lower alkoxy andacetylamino.

It is further preferred that R represents the ,B-chlorm ethyl radical.

It is also preferred that Y and Y each represent a B-hydroxyethylradical.

A third preferred class of the monoazo dyestuffs of the inventioncomprises the monoazo dyestuffs which are represented by the formula:

wherein Z and Z are each independently selected from the classconsisting of hydrogen and chlorine; and Z is selected from the classconsisting of hydrogen, lower alkyl, lower alkoxy, chlorine, bromine andacetylamino.

The invention is illustrated but not limited by the following examplesin which the parts and percentages are by weight.

Examples 1 A solution of 6.9 parts of sodium nitrite in 50 parts ofwater is added gradually to a solution of 27.1 parts of 4an1inobenzenesulphon-N-(fi-chloroethyl)amide hydrochloride in a mixtureof 400 parts of water and 15 parts of a 36% aqueous solution ofhydrochloric acid at a temperature between 15 C. and 20 C. The solutionso obtained is added during 20 minutes to a solution of 16 .5 parts ofNethyl-N-,B-hydroxyethylaniline in a mixture of 200 parts of water and11.2 parts of a 36% aqueous solution of hydrochloric acid at atemperature between C. and C. After stirring the mixture for 2 hours itis neutralized to Congo red by adding 55 parts of a 30% aqueous solutionof sodium acetate slowly over '30 minutes. After 5 minutes the insoluble4-(fi-chloroethyl) aminosulphonyld' Nethyl-N-(B-hydroxyethyDaminoazobenzene is filtered off, Washed withwater and dried.

1 part of the product so obtained is dispersed in 20 parts of water bymilling in the presence of a sodium salt of a sulphonated naphthaleneformaldehyde condensation product and the dispersion so obtained isadded to 4000 parts of water containing 4 parts of a condensate ofethylene oxide with a fatty alcohol. 100 parts of nylon (polyamide)textile material are placed in the dyebath so obtained and the dyebathis then heated to 95 C. and maintained at that temperature for 60minutes. The nylon fabric is then rinsed in water, immersed for 30minutes in a hot aqueous solution containing 0.2% of sodium carbonateand 0.1% of a condensate of ethylene oxide with an alkyl phenol, againrinsed with water and dried. The polyamide textile material is dyed toan orange shade of very good fastness to washing.

Polyhexamethylene adipam ide or polycaprolactam may be used as the nylon(polyamide) textile material in this example and throughout thefollowing examples.

If the polyamide textile material is replaced by 100 parts of secondarycellulose acetate and the dyebath is heated at 85 C. for 60 minutes thecellulose acetate is dyed to an orange shade.

Example 2 The 16.5 parts of N-ethyl-N-/3hydroxyethylaniline used inExample 1 are replaced by 19.5 parts of N:N-di(fl-hydroxyethyl)-m-toluidine. 4 ([3 chloroethyl) aminosulphonyl-Zmethyl-4-N :N-di(fl-hydroxymethyl) aminoazobenzene is obtained whichdyes secondary cellulose acetate in orange shades and polyamide textilematerials in orange shades of very good fastness to washing.

The degree of fixation of the dyestuff on the dyed nylon is determinedas follows:

The dyed polyamide textile material is successively extracted withn-propanol at 85 C. until no more dyestuff is removed from the nylon onfurther treatment with n-propanol. The quantity of dyestufi remaining inthe polyamide textile material is then found by dissolving the polyamidetextile material in o-chlorophenol and determining the dyestufr'colorimetrically. Comparison with the quantity of dyestutl found in thesame way to be present in an identical Weight of similarly dyedpolyamide textile material before extraction with n-propanol gives thedegree of fixation as 69%.

In a similar test on polyamide textile material dyed with4-(beta-hydroxyethyl)aminosulphonyl-2-methyl4'- N:N-di(betahydroxyethyl)aminoazobenzene the whole of the dyestufi' was extracted bythe n-propanol at 85 C.

Example 3 30.55 parts of 3-chloro-4'aminobenzenesulplion-N-dchloroethylamide hydrochloride are dissolved by warming in a mixture of200 parts of acetic acid and parts of a 36% aqueous solution ofhydrochloric acid and the solution cooled to a temperature between 15 C.and

C. To the suspension so obtained is added over 10 minutes a solution of6.9 parts of sodium nitrite in 50 parts of water. 200 parts of water arethen added and the resulting suspension of diazonium compound is addedover 20 minutes to a solution of 19.5 parts of N:N-di(,8-hydroxyethyl)-m-toluidine in a mixture of 180 parts of water and 18parts of a 36% aqueous solution of hydrochloric acid at a temperaturebetween 0 C. and 5 C. The mixture is stirred for 30 minutes, neutralisedto Congo red by slowly adding 70 parts of a 30% aqueous solution ofsodium acetate and then stirred for a further 5 minutes. 2chloro-4-(ti-chloroethyl)am-inosulphonyl- 2-methyl-4:N:N-di(,8hydroxyethyl)aminoazobenzene so obtained is then filtered off, washedwith water and dried. When dispersed in aqueous medium it dyes secondarycellulose acetate to reddishorange shades and polyamide textilematerials to scarlet shades of very good fastness to washing.

The fixation of the dyestufi on the dyed nylon is 69%.

Example 4 A solution of 6.9 parts of sodium nitrite in 50 parts of wateris added gradually to a solution at 10 C. of 27.1 parts of3-aminobenzenesulphon-N-(p chloroethyl)amide hydrochloride in a mixtureof 480 parts of water and 15 parts of a 36% aqueous solution ofhydrochloric acid. The resulting solution is added during 10 minutes toa solution of 18.1 parts of N:N-di(fi-hydroxyethyl)aniline in a mixtureof 200 parts of water and 10 parts of a 36% aqueous solution ofhydrochloric acid at a temperature of between 0 C. and 5 C. The mixtureis neutralized to Congo red by the addition of 50 parts of a 30% aqueoussolution of sodium acetate and after 12 hours the resulting dye isfiltered 01f, washed with water and dried. When dispersed in aqueousmedium it dyes polyamide textile materials in orange shades of goodfastness to washing.

Example 5 The 18.1 parts of di(fi-hydroxyethyl)aniline used in Example 4are replaced by 19.5 parts of N:N-di(fihydroxyethyl) m toluidine.3-(l3-chloroethyl)aminosulphonyl-2-methyl-4-N:Ndi(/5'-hydroxyethyl)aminoazobenzene is obtained which dyes polyamidetextile materials in orange shades of good fastness to washing.

Example 6 27.1 parts of 4 aminobenzenesulphon N-(fl-chloroethyl)amidehydrochloride are diazotised according to the method of Example 1 andthe resulting solution is added during 20 minutes to a solution of 19.9parts of N-fl-cyanoethyl-l-naphthylamine in 800 parts of acetone at atemperature between 0 C. and 5 C. The mixture is stirred for minutes andthen neutralized to Congo red by slowly adding 25 parts of a 30% aqueoussolution of sodium acetate. The dyestuff is filtered off, washed withwater and dried. When dispersed in aqueous medium it dyes celluloseaceate rayon in orange shades and polyamide textile materials in scarletshades of very good fastness to washing. The fixation of the dyestufi onthe dyed polyamide textile material is 68%.

Example 7 A solution of 6.9 parts of sodium nitrite in 50 parts of wateris'added to a solution of 27.1 parts ofZ-aminobenzenesulphon-N-(fl-chloroethyl)amide in a mixture of partsofacetic acid and 4 parts of a 36% aqueous solution of hydrochloric acidat a temperature between 10 C. and 15 C. The solution is stirred for 15minutes and then added during 20 minutes to a solution of 19.5 parts ofN :N-diQS-hydroxyethyl)m-toluidine in a mixture of 200 parts of waterand 12 parts of a 36% aqueous solution of hydrochloric acid at atemperature of between 0 and 5 C. The mixture is stirred for 2. hoursand then neutralised to Congo red by slowly adding 40 parts of a 30%aqueous solution of sodium acetate. The dyestuff is filtered ofi, washedand dried. When dispersed in aqueous medium it dyes polyamide textilematerials in orange shades of excellent fastness to washing and wool inorange shades of good fastness to washing and millin".

Example 8 A solution of 6.9 parts of sodium nitrite in 50 parts of wateris added during minutes to a solution of 30.1 parts of4-aminobenzenesulphon-N-('y-chloro-p-hydroxypropyl)amide hydrochloridein a mixture of 375 parts of water and parts of a 36% aqueous solutionof hydrochloric acid at a temperature of between 5 and 10 C. Thesolution so obtained is added during minutes to a solution of 19.5 partsof N:N-di(fi-hydroxyethyl)-mtoluidine in 250 parts of water and 15 partsof a 36% aqueous solution of hydrochloric acid at a temperature of 0 and5 C. After stirring the mixture for 2 hours it is neutralised to Congored by adding 62.5 parts of a 30% aqueous solution of sodium acetateslowly over 30 minutes. The insoluble product is filtered oif, stirredfor 30 minutes in 400 parts of water which have been made alkaline tolitmus by the addition of sodium carbonate, filtered off, washed withwater and dried. 4-(y-Chl010- ,B-hydroxypropyl) aminosulphon 2' methyl4' NzN- di(,8-hydroxyethyl)aminoazobenzene is obtained which has verygood build-up properties on polyamide textile materials giving orangeshades of good fastness to washin".

8 Example 9 A solution of 6.9 parts of sodium nitrite in 50 parts ofwater is added gradually to a suspension of 26.9 parts of4-amino-3-chlorobenzene sulphon-N-([i-chloroethyl)- amide in a mixtureof 400 parts of water and 25 parts of a 36% aqueous solution ofhydrochloric acid at a temperature between 5 and 10 C. The suspension soobtained is then added during 20 minutes to a solution of 19.6 parts ofN-B-cyanoethyl-l-naphahylamine in a mixture of 512 parts of acetone and12 parts of a 36% aqueous solution of hydrochloric acid at a temperatureof between 0 C. and 5 C. The mixture is stirred for 2% hours, 68 partsof a aqueous solution of sodium acetate are added, the mixture thenstirred for a further 16 hours 6 parts of the sodium acetate solutionadded. The precipitated dyestuif is then filtered, washed with water anddried. When dispersed in aqueous medium it dyes polyamide textilematerials in red shades possessing excellent fastness to washing.

The following table gives further examples of monoazo dyestuffs of theinvention which are obtained by diazotising the amines listed in thesecond colunm of the table and coupling the resulting diazo compoundswith the coupling components listed in the third column of the table bymethods similar to those described in the previous examples. The fourthcolumn of the table gives the shades obtained when the dyestuffs areapplied to polyamide textile materials.

Example Amine Coupling Component Shade4-aminobenzenesnlphon-N-(fl-ehloroethyl) amide Reddish-orange.

Reddish-yellow.

Yellowish-orange.

(B-hydroxyethyl)-1-naphthylamino Red. -hydroxyetl1yl)-2-naphthylamine.Red.

Orange.

-hydroxyethyl) -N- (B-eyanoethyl) aniline Red sh-yellow. Red.

s e. l-N-fl-hydroxyethylamiuo-S:8-dichloronaphtl1nlone Red.

d0 l-N-B-hydroxyethylami11o-4-chlor0napl1thalene PinZ-ethoxy-l-naphthylamine Bluish-red.

4-a1nino-3-chl0robenzenesulphon-N(fl-chloroethyD-N:N-di(B-hydroxyethyl)amino-2-methoxy-fi-methyl- Red.

amide. benzene.

N-(B-hydroxyethyl)-N-(fi-cyanoetliyl)aniline Orange.

2-ethoxy-1-naphthylamine Roddish-violet,l-N-(B-hydroxyethyl)amino-4-chloro-naphthalene Bluish-red. oN-(fl-ethoxyethyl)N-(ficyanoethyl)-m-toluidine Orange.2-anisiline4-sulphun-N-(' 'chloro fi-hydroxypropyl) N N-di(fl-hydroxyethyl)-m-t0luidine D0.

ann e. Z-anisidineA-sulphon-N-(fl-chloroethyl)amideN-fl-hydr0xyetl1yll-naphthylaniine Red. 4-amir(110benzenesulphon-N-(B:y-diehloropropyh-N:N-di(B-hydroxyethyl)m-t0luidine Orange.

ami e. 2 aminoi-triiluoromethylbenzene-sulphon-N-(fld0 Scarlet.

chloroethyl) amide. 4-aminiobenzenesulph0n-N-(v-bromo-fl-hydroxypropyl)do Orange.

ann e. 4-aminobenzenesulphon-N- (B-br0moethyl) amide do D o.2aminobenzenesulplion-N-(B-chloroethyl)amideN-(B-hydroxyethyl)lnaphthylamine Red.2-amino-4-trifluoromethylbenzene-sulphon-N-( 8- ..--.do Red.

ehloroethyDamide. 3-aminobenzenesulphon-N-(- chloro-fl hyrlroxy-N:N-di(fl-hydroxyethyl)-m-toluicline Orange.

propyDarnide. -amircilobenzenesulphon-N-(B y-dibromopropyl) .do Do.

ann e. 2:5-dichloro-4-aminobenzenesulphon-N-(fid0 Red.

chloroethyl) amide. 4-a1ni 1(1io-3-bromobenzenesulphomN-(Bcl1loroethyl)..d0 Scarlet.

ann e. 4-amino-3-chloro-5-methylbenzenesulphon-N-(fld0 Orange.

chloroethyDamide. 4-amino-3:5diehlorobenzenesulphon-N-(B- .d0-Yello\vishbrown.

chloroethyl) amide. 46 4en1inobenzenesulphon-N-(B-ehloroethyl)amideN:N-diQShydroxyethyl)amino-3-chlor0benzene Orange 474amin1o3-chlorobenzenesu1ph0n-N-(Bchloroethyl)N:N-di(fl-acetoxyethyl)-m-t0luidine Reddish-orange.

amt e. (lo N:N-di(flhydroxyethyl)-m-anisidine Do. 49 minoenzenesulphon-N-(B-ehloroethyl)-amide N:N-diethyl-m-toluidine- Orange.50 d0 N-methyl-m-toluidine... D0. 51l-naphtl1yla1ninc-4-sulpl1on-N-(fl-chloroethyl)amideN:N-di(6-hydroxyethyl)-n1-toluidme Red. 522-naphthylamine-5-sulphon-N-(B-chloroethyl)amide Orange. 532-naphthylamine-fi-sulphon-N (fl-chloroethyDamide. -..do. Do. 544aminohenzenesulph0n-N(fl-ehloroethyD-amideN:N-di(B-hydroxyethyl)-3-bromobenzene Do. 55 doNIIJN-di(fi-hydroxyethyl)amino-3-acetylamino- Do.

enzcne.

Scarlet.

Maroon. Reddish-orange. Red

Reddish-orange.

Bluish-red.

wherein A is an arylene radical selected from the class consisting ofphenylene and naphthylene radicals and any further substituents on saidphenylene radical are selected from the class consisting of chlorine,bromine, lower alkyl, lower alkoXy and trifluoromethyl;

R is selected from the class consisting of B-chloroethyl,

B-bromoethyl, fiz' -dichloropropyl, Bry-di bromopropyl,'y-chlorofi-hydroxypropyl and 'y-brorno-fi-hydroxypropyl;

B is an arylene radical selected from the class consisting of1:4-phenylene, 1:4-naphthylene and 1:2 naphthylene radicals, and anyfurther substituents on said arylene radical are selected from the classconsisting of chlorine, bromine, lower alkyl, lower alkoxy andacetylamino;

Y is selected from the class consitsing of hydrogen, lower alkyl,hydroxy lower alkyl, acetoxy lower alkyl and ,B-lower alkoxy ethyl;

and Y is selected from the class consitsing of hydrogen,

lower alkyl, hydroxy lower alkyl, B-aminoethyl, flcyanoethyl and acetoxylower alkyl.

2. Monoazo dyestuffs as claimed in claim 1 wherein Y and Y eachrepresent the B-hydroxyethyl radical.

3-. Monoazo dyestuffs as claimed in claim 1 wherein A is a phenyleneradical and the -SO NHR group is attached to A in para postion to theazo group.

4. The monoazo dyestufis of the formula:

wherein Z and Z are independently selected from the class consisting ofhydrogen and chlorine; and Z is selected from the class consisting ofhydrogen, chlorine, bromine, lower alkyl, lower alkoXy and acetylamino.

References (Iited by the Examiner UNITED STATES PATENTS 2,766,231 10/1956 Bolliger 260163 3,050,516 8/ 1962 Merian et al. 260-405 3,154,5338/1964 Eisele et al 2 -199 X FOREIGN PATENTS 664,258 1/1952 GreatBritain.

CHARLES B. PARKER, Primary Examiner. FLOYD D. HIGEL, Assistant Examiner.

1. THE MONOAZO DYESTUFFS OF THE FORMULA: